JPS6037680A - Electrochemical device - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION This invention relates generally to electrochemical devices, and more particularly to gas relief valves for closed cell compartments in metal-halogen battery stacks. PRIOR ART AND PROBLEMS OF THE PRIOR ART Electrochemical devices or systems of the type referred to herein include many metal halide battery systems, such as zinc chloride battery systems. These metal halogen batteries 'JA Direct' generally have three basic parts'
C drawing configuration, line electrode stack section, electric FN ¥!
It consists of a storage subsystem and a storage subsystem. The electrode stack sections are typically electrically connected in various series and parallel combinations to scale the desired operating voltage and current at the battery terminals during charging/discharging battery recycle. /V
I'm here. Each cell is comprised of one anode electrode, one cathode electrode, etc., both electrodes being in contact with a metal halide electrolyte. The electrolyte circulation subsystem provides for replenishing the ionic components of the metal and halogen electrolytes from the Iri' tank as they are oxidized or removed within the cell during the battery cycle. Operation 1 is performed to circulate the metal chloride electrolyte through each cell in the electrode stack. In a sealed self-contained metal-halogen battery system, the storage rib system stores the halogen gas or liquid released from the battery during charging of the battery system and stores the halogen gas or liquid released during discharge of the battery system. Used to return to battery. In zinc chloride battery equipment, the

[J, released from the anode of a cell and stored in the form of chlorine hydrate. Chlorine hydrate, which contains chlorine in ice crystals, is a solid formed by the storage subsystem in a process similar to that of freezing water. In terms of general operation of the zinc chloride battery system, the electrolyte pump operates to circulate the zinc chloride electrolyte from the reservoir to each of the anodes or chlorine J electrodes in the electrode stack. The electrolyte is made of porous graphite, and the electrolyte is of the chlorine type (through the 6 pores,
It flows into the space between the pole and the opposing cathode or "zinc" electrode. The electrolyte then flows between the opposing electrodes or out of the cells in the electrode stack and returns to the electrolyte reservoir or sump. During charging of a zinc chloride battery device, metallic zinc adheres to the surface of the zinc electrode base, and chlorine gas (well, chlorine gas) is liberated or generated. J! The sludge is collected in the conduit 21 and mixed with the cooled liquid. , the brine gas is pulled from the electrode stack and the cold IJ+ liquid (7
A gas pump is typically used to mix the electrolyte (i.e., generally zinc chloride electrolyte or water). The frozen chlorine is deposited in the storage container until such time as the battery device is discharged. During discharge of a zinc chloride battery device, frozen chlorine is stored by circulating a warm liquid through a storage vessel. It is decomposed by changing the crystallinity to FW. The chlorine gas recovered in this way is returned to the main stack by the electrolyte circulation V-bu system and converted to 39 yuan at the chlorine electrode.Metal zinc is melted from the zinc electrode substrate and the battery Power is available at the terminals. Charging/discharging of zinc chloride batteries (During the course of a neucle, the concentration of the electrolyte changes as a result of the electrochemical reactions that occur at the electrodes of the cells in the electrode stack. Charging/discharging of zinc chloride batteries. From U11 to 8J, chloride ill in the electrolyte
: The 8) degree of 4i+ may typically be 2.0[l]. As the charging part of the recycling process, the electrolyte concentration [
, 1. Zinc ions and the like will gradually decrease as they are depleted from the electrolyte. Once the battery device is fully charged, the electrolyte concentration is typically 0.5
decreases to moles. Then, as the battery is discharged, the electrolyte concentration increases to the next level until the device is fully discharged.
It returns to the 2.0 molar concentration at the end when it is discharged for ζ'-min. A more detailed description of the cross-body operation of zinc chloride battery devices can be found in the following, similarly assigned special notes, U.S. Pat. No. 37,138 to Simmons.
No. 88 [Method of obtaining electrical energy using solid halogen hydrates]. Simmons, US Pat. No. 3,809,578, ``Methods for forming halogen hydrates in batteries''. Mr. Carr et al.
``Batteries with vented electrodes and their usage''. Mr. Kerr's US IF No. 4100332 ``Comb-shaped 24-cell element and its battery stack''. Those devices are also described in the following publications prepared by the assignee of the present invention: [Opening of Zinc Chloride Batteries for Useful Applications J, May 1980, Interim Report FM
-1/117゜[Development of Zinc Chloride Batteries for Useful Applications, April 1979, Interim Report EM-1051゜All, Elek 1, Ba D Al 1-City, California.
Link Power Relief Instrument: Prepared for L-1~. Specific references to the above cited documents are incorporated herein by reference. During operation of the zinc chloride battery device, it is not possible for some hydrogen to be generated from the zinc electrode substrate. The equilibrium potential of metallic zinc in a zinc chloride aqueous solution is J
1, the release of hydrogen gas from pure zinc metal is very low due to the high overvoltage present in hydrogen. ) However, this /lk output rate is due to the morphology of zinc4.
1y! However, the rate of hydrogen release that occurs at the salt electrode during charging of the battery device a is governed by several factors, including the presence of hydrogen in the H precipitate. Hydrogen emissions are typically very small compared to gas emissions.Due to the fact that aqueous emissions result in poor electrical efficiency, reducing the It is important that hydrogen gas in the battery stack be reduced by reacting with chlorine gas after its generation. Fussa Zinc Battery Equipment In iJ, a controlled chemical reaction of fluorine gas and hydrogen gas is achieved by applying 1' or 2(4) light beams with wavelengths of light radiation in the ultraviolet range. During the charging of the zinc chloride battery pack, the chlorine gas and hydrogen gas generated by the multiple cells are illuminated by an ultraviolet light source to form hydrogen chloride. During discharge of the device, chlorine gas and optionally hydrogen gas, which may be present in the gas space in the stack area above the plurality of cells, are also illuminated by this source of ultraviolet light. [Problems to be solved] In the prior art chloride 11 lead battery stack installation J1, the unit cells of the battery are housed in the receiving area, or the chlorine scum and hydrogen scum are discharged from the 111 battery. However, according to the present invention, the cell CJ1 of the battery is arranged substantially within the cell compartment. , this compartment includes a mouth section for controlling both the inflow and outflow of electrolyte into the cell compartment and the venting of gases from the cell compartment. In other words, it is possible to capture the gas that forms in the gas space above the cell in the cell compartment in the fixed state.
It is. After the battery device is charged, hydrogen gas continues to be generated at the zinc electrode in the cell compartment in the waiting area. It can be stored in the battery compartment. And the battery device δ
When the discharge begins, the stored hydrogen gas in the cell compartment is discharged from the compartment and becomes a source of ultraviolet light at a certain rate as the chlorine gas exceeds the desired level. 1M is falling. Accordingly, it is a primary object of the present invention to provide an improved electrochemical device cell stack design that is capable of selective IJI extraction of gas from a plurality of cells. To provide an improved battery stack arrangement H1 capable of automatically discharging gas from a single cell at a predetermined time without relying on any electrical control. This is a more specific object of the present invention. It is another object of the present invention to provide an improved cell design for a zinc chloride battery device in which hydrogen gas is emitted from the cell during charging and standby conditions. , the present invention provides a reservoir device defining a substantially closed compartment containing a cell of a battery and at least a portion of an electrolyte for a Xali pond device; An improved battery stack HH1 is provided that features a compartment device and associated devices for selectively IJI venting gas from within the compartment device in response to levels. It includes a relief valve having a flow 1 to 811 actuated in response to the electrolyte level. , the relief valve is opened once the electrolyte level is below this predetermined level.Additional advantages of the present invention include the following. It will become clearer after reading the detailed description of the preferred embodiments thereof with reference to the drawings. A side view and a front view of a zinc chloride battery device 10 according to an embodiment of the invention are shown.The main components of this battery device 10 are as follows:
Two phase Ti bonded cylindrical containers 12d3 and 14
The situation is best illustrated by the schematic diagram in FIG. A sub-container or case 12 is used to house a chlorine hydrate storage system, generally designated by the reference numeral 16. The lower container J or case 14 is a battery stack 18
and an electrolyte circulation sleeve system indicated by the reference numeral 20. The cylindrical containers 12 and 14 are located on the battery shelves 41'4 and 22.
Supported by Container 12 a3J: and 14 is b
Preferably, they are manufactured from fiberglass-reinforced plastic deck (FRP) and have an inner surface that is chemically resistant or inert to the electrolytes and other chemicals within these containers. 1 internal polyvinyl resin [1 side (+) V C) liner is bonded. Vessels 12J3 and 14 are connected by four-way fluid exchange tubing or guides 24, 26, 28 and 30, and the direction of fluid flow through these pipes is indicated by appropriate arrows. . Furthermore, the battery device 10
1, four refrigerant pipe systems or conduits 32, 3, 4, 36, and 38 are installed. Refrigerant piping systems 32 and 34 are used to supply refrigerant to storage subsystem 16 during battery charging to reduce the temperature within vessel 12 to a suitable level to form chlorine hydrate. Ru. Refrigerant piping systems 36 and 38 G; l, for supplying refrigerant to the IJ electrolyte reservoir 40 in the sump of the decomposition circulation subsystem 20 to control the temperature of the zinc chloride electrolyte; used. Next, the electrolyte circulation system 20 will be explained with reference to FIG. 2 J3 and FIG. 3. Electrolyte circulation→knob system 20 includes an egg-shaped electrolyte pump P1, which pump [
It is mounted on the front end plate 42 of the lower container 14 below the 'Jfi decomposition level in the liquid reservoir 40. Electrolyte pump P1 is driven by an electric motor 44 that is magnetically coupled to the pump. Electrolyte pump P1 is preferably of the rectangular, centrifugal type manufactured by Ingersoll Rand. Electrolyte pump P1 draws lightning YfVa from a reservoir 40 through a titanium protective screen filter 46 and axially pumps the electrolyte through a slip fitting 58 into a unique center-fed electrolyte distribution manifold 50. 111 is out. This manifold 50 is used to distribute electrolyte to each of the cells in a pair of submodules 52, 54 to the right of the cell stack 18. The manifold 50 not only distributes the electrolyte evenly to each of the cells within the submodules 52 and 54, but also controls and suppresses the flow of parasitic currents within the electrolyte circulation subsystem.
It works like a sea urchin. Anomalous current is a current that flows in a conductive path created by the electrolyte and the workpiece. A remarkable improvement in the suppression of the 1-current was surprisingly achieved in combination with the direct current, which will be explained in more detail below.With reference to FIG. 5 is a schematic diagram of one embodiment of the subsystem 20, specifically illustrating the flow of electrolyte through the manifold 50. Referring also to FIG. 6 and 7 illustrate two views of a manifold 50, which includes a pair of concentric tubes, an inner tube 58 and an outer tube 60.
and a central portion 56 having a central portion 56. The inner tube No. 58 is in communication with the electrolyte pump P1 at its first end 62, and the wire mesh electrolyte filter 66 on the line is connected to the open IC opposite end 64G. The filter 66 includes a porous protective envelope 68 terminating in a cap or plug 70 at its distal end.The electrolyte is routed through the inner tube 58 and through the filter 66 to the outer tube 60. Mt enters into the vertical side pipe 60, 9ν
1: Part 2 I knob 72 is glued together, and this end key A7 knob guides the fluid through the inner end 4 = around the V knob 70 and into the special pipe 76. The machine conduit 76 (J3 and 1) is stopped at the end plate 78, including /υ,
A pair of handles for branching the electrolyte fluid oil 11 into two.
Includes holidays 80 and 82. In the same manner, the outer tube 60 further includes a pair of fittings 84 and 86 at the end close to the electrolyte pump 1]1 in the other two-branch fluid passage G"Ij l]Z)1 knee. In this way, the electrolyte contains
Through filter 66 and pumped into outer tube 60, half of the fluid passes through tube 76 to electrolyte pump P1.
while the other half is routed through the outer tube 60 as a whole towards the electrolyte pump P1. Mounting body 80.82 and handle 84°86
In the left half of the two submodules 52 and 54, the flow of electrolyte is divided into four distribution passages.
Lightning F17'a is separately supplied to both the left hand and the right hand. With particular reference to Figure 4, intersecting inlet distribution pipes! Describe the device. Figure 4 shows J, sea urchin, example GlK, distribution pipe 8
8 is connected to the fl body 82 and feeds the left half 90 of the ribmodycol 54, which is substantially further from the fl body 82 than the 4i 4' portion 92. Similarly, the handle 86 is connected to the right hand portion 92 of the one-knob module 54 via a distribution pipe 94. Accordingly, the electrical circuit path between the left and right passages of the submodule 54 becomes quite long, providing significant resistance to parasitic current flow. For example, the Rj live current flow between the cell supply tubes 96J3 and 98 requires the tube 88, the handle body 82, the tube 76, the outer tube 60, the handle body 8G and It must pass through tube 94. The length of this short circuit (so long that its electrical 11 (although high resistance), the fluid circuit described above, including the crossed inlet distribution pipes 88 and 94, is non-conductive to the electrolyte pump 1] Therefore, the electrolyte pump I) 1 can be of relatively low horsepower, thereby improving the overall efficiency of this battery arrangement. The embodiment of FIG.
This is to increase the electrical resistance to the flow of parasitic currents, as described above with respect to No. 4. As can be seen with reference to FIG.
0 and 92 intersect outlet tubes 100 and 102, respectively, in a manner similar to the cross-coupled central feed inlet section. At the exit portion of the electrolyte circulation system 20, an IR-shaped tenyo 104 can be used as shown in FIGS. 3 and 5. 11 of this selection] In the case of J5, each individual cell has an exit hole 106.
The electrolyte then passes through the discharge 108 and exits the IJI on the step-like surface of Ki 104 through the discharge 108. Flowing over the canopy 104 and spreading outward from the drain/j into the sump 40, it improves the absorption of gaseous chlorine by the electrolyte in the discharge quill.The manifold 50 and inlet cross-distribution system. The crossing collection pipe arrangement at the outlet is referred to as the center feeding principle or arrangement. This can be explained in detail with reference to the actual state of electrolyte distribution in the conventional technique 1.3. In the conventional technology J Fussa zinc battery device, the electrolyte is connected in series. A continuous wood manifold or distributor is typically fed to each cell in a module, typically through a common header. The header has a relatively low electrolyte resistance from one end to the other.This end supply arrangement will generate relatively large parasitic currents in short circuits between virtually any cells in the submodule. In contrast, the electrolyte distribution system shown in FIG. (For example, pipes 60 and 76 in manifold 50
or by pumping (or suctioning) each half flow through population distribution pipes 88J5 and 94), a single 1-knob module consisting of a number of cells connected in white rows (
For example, the electrolyte is supplied to the sub module 54, etc.). Compared to the large current that exists between the common electrolyte-supplied halves of the 1-knob module, the 4th All of the short circuits shown in the figure that exist between the separately supplied Ffl fluid halves of the submodule have been dramatically reduced. Therefore, 1. In short, this central supply arrangement is:
It can be said that any of the following 61 electrolyte distribution steps are also included. In that 61 car, the flow of electrolyte flowing into a single bumodicol consisting of a number of cells connected in series was divided into equal parts (two or more), and then In order to distribute (or collect) a generally small electrical resistance b'L through two separate electrically insulated headers, each header has multiple supplying electrolyte to 111 cells connected in series or collecting electrolyte from single cells);
Parasitic currents generated in the cell-to-cell circuit between the separately supplied electrolyte portions of a one-knob module are significantly reduced compared to an end-fed electrolyte distribution arrangement. The electrical fluid circulation (knob system 20) of the battery assembly disclosed herein incorporates the central supply principle described above and utilizes a central supply arrangement to advantageously reduce parasitic currents. The effectiveness of the above center-fed electrolyte distribution arrangement is illustrated by reference to Figure 8. 2 is a diagrammatic representation showing the value of a typical short circuit or parasitic current shown along the vertical axis as a function of the cell number shown. For illustrative purposes, three cells electrically connected in series are shown. 0
Although it shows a battery with a li battery,
The same advantageous result can be obtained even with a battery having an i:1 number of cells electrically connected in series! I
! should be understood. As mentioned above, all of the cells making up the battery are supplied with electrolyte by a single electrolyte pump via common supply and return piping -C
There is. This common electrolyte distribution 73 is an electrically conductive path through which current flows when voltage is present at the battery terminals and the electrolyte circulation subsystem 20 containing the battery stack is filled with electrolyte. We provide. This short-circuit current reduces the effective current flowing through the cell during charging 111''I, and causes self-discharge of those cells within the cell during discharge at various discharge rates.Generally , this results in rapid depletion of the electrodes of the single cells in the center of the battery stack, and a measurable difference in the electrical charge of the number of single cells in the battery stack.
can occur. Once the resistivity of the electrolyte and the dimensions of each part of the electrolyte circulation rib system 20 are known, the effective electrical resistance of the various parts can be determined. Therefore, an equivalent electrical circuit model can be constructed if desired. For example, U.S. Patent No. 1 of Chii et al., February 1, 1983 entitled ``Yoshii: Method for Reducing the Effects of Electric Current''!
No. 371825 Akigawa i! ), so it is quoted here for reference. FIG. 8 is a graph comparing the values of odd currents during charging based on such an electric circuit model. Figure 8 song PI! 112 is a Nokoden Il! with a prior art end-fed electrolyte distribution manifold. ! Device Niri J-! J
Curve 114 (114) shows an odd current component (b) of a battery assembly according to the present invention having a center-fed electrolyte distribution manifold.
The parasitic current distribution for ′j is shown. Note that not only is the total parasitic current for curve 112, IN, greater than the total parasitic current for curve 114, curve FA114 is also less parasitic when a center supply manifold is used. It shows that the current components b are significantly more even. This advantage of a center feed manifold is a positive one. Above all, it is desirable to minimize the flow of parasitic currents throughout the battery stack in order to achieve approximately equal electrical efficiency for each of the cells in the battery stack. Equivalent portion of the strange current
This is because it is desirable to obtain Turning to FIG. 9, an exploded view of a zinc chloride battery electrode assembly 200 is shown, which forms the basic building block of the battery stack 18. The electrode assembly 200 generally includes a pair of porous graphite anodes or chlorine electrodes 202 and 204 and a dense graphite 112 electrode or zinc type (20
6 and plastic frame members 208 J5 and 210. Anode electrodes 202 J5 and 204 are adapted to slide within fR212 and 214, respectively, in frame member 208, and the frame member connects these two electrodes to one of its side edges and one section above and below it. Support along the frame member 20
8 acts to align the anodic electrodes 202 and 204 in parallel, forming an internal space between these electrodes. The frame member 208 also connects the frame member 210 to the positive 41A electrode 20.
2. It is formed to be supported by inserting 1Φ between J3 and 204. Frame member 210 includes a plusbook supply 216 for transporting electrolyte from one cell manifold to the interior space between anode electrodes 202 and 204. Frame member 208
Also, a groove 218 is formed, and this vortex is connected to the cathode electrode 206.
The side edge of the cathode electrode 206 is inserted into the anode type 14
i 202 so that they are aligned parallel to each other. Therefore, while aligning and separating frame member 208 G; J, anode electrodes 202, J: and 204 from each other, also
06 to the anode type (202), then separate it!
It will be understood that the azuru J will act on the sea urchin. r
The gap between the bipolar electrode 206 and the anodic electrode 202 is described as the air gap between the electrodes, which typically ranges from about 1 mm (40 mils) to about 6 meters (250 mils);
Preferably it is about 3.3 mm (129 mils). This frame member 208 also includes the anode electrodes 202 and 20.
To modify the electrochemical activity along the edges of the anodic electrodes 202 and 204 111+
11111 acts on the sea urchin. Generally speaking, full 2
12.214 and 218 are formed such that the apparent surface area of the anodic electrode is small compared to the apparent surface area of the cathodic electrode. A more detailed explanation of the edge ell shielding effect is found in similarly assigned U.S. Pat. No. 4, Carr et al.
No. 241150 1 - Method for controlling edge effects in oxidizer electrodes. The frame member 208 has one opening 220 in the IA portion of the frame member to drain out undissolved chloride scum that would otherwise remain in the internal space between the anode electrodes 202 and 204. It should also be noted that Additionally, frame member 208 is formed with a pair of opposing vertically extending spacing ribs 222 and 224. The ribs 222 and 224 are connected to the anode electrode 202 J5.
The tendency of Jζ and 204 to curve outward is suppressed to maintain the required interelectrode gap between the anode and cathode. It is important that the gap between the electrodes is perfect.3.
When the air gap increases to about 3 mm (129 mils), the current density for the battery device becomes Jl'111+1-! I
Because it is possible. Also, since such an increased void space accommodates an increase in the zinc loading m on the cathode electrode, this therefore leads to a reduction in the number of electrodes required to store an equivalent 1d of electrical energy. J means that substantial cost savings can be achieved. Electrolyte 4JI supply tube 216 of electrode assembly 200 is connected to a socket formed in upwardly extending protruding portion 226 of frame member 210. The lower end of the supply tube 216 is also held between a clip portion 228 extending above the frame illumination 210 and a support groove portion 230. It should also be noted that is frame member 2
The lower end of the supporting portion 230 of No. 10 is formed in a shape that fits into the lower end of the portion 232 that isolates the anode inside the frame member 208. This contour shape, which is located at the lower end, is similar to the 44' section 1 of the frame member 210 (approximately horizontally extending flange section 234) that falls on the IΩ section.
4210 is fixed to the frame [208]. Regarding the materials used to construct electrode assembly 200, anodic electrodes 202 J3 and 204 are made of Corni A
PG-60 or TS-1697 Graphite from Carbon Carbide Corporation electrode 206
This electrode has an ECL rating of 1 to 1 or △1 for union carbide.
R or other grades such as ATJ (preferably 14). Regarding frame members 208 and 210?3'216,
These components (as well as other positive components described below) are chemically resistant to catalytic electrolytes and other chemicals (resistant or inert to any suitable electrically conductive material). Frame members 208 d3 and 210 may be made of General Tire & Rubber Corporation's Voltaron™ polyvinyl chloride or tYBF Gudridge.・Preferably composed of ZEON (trademark) polyvinyl 11-ride manufactured by Zeon Corporation;
16 (Well, DuPont's Teflon <quotient 4 votes) (Bolide 1~
Preferably made with rough J and A mouth・”-jiren)
However, other suitable plus deck monthly rates, such as Benwald Kayna™ (polyvinylidene fluoride) or previously reported T+1 [approved 1 979 s
tAy'+ (described in Section 4 of ``Development of Zinc Chloride Batteries for Utilization Applications'' in April, IJ et al. as appropriate) may be used. Referring to Figure 10,...J Fussa! lI! An exploded view of one "disassembled" one-knob module 236 for use in a fil battery stack is shown. This rib shiji
- The rule 236 generally includes an IL lead terminal type body 238, a chlorine terminal comb type body 240, and a 1 fl
+, 1j, and more bipolar intermediate comb assemblies 242
1. The knob module 236 is shown as having only one intermediate comb assembly 242; however, the knob module 236 is enlarged with () to provide more intermediate comb assemblies. That is understood. As shown in FIG. 10, the submodule 236 includes two "unit" cells electrically connected in series. Each of these cells has a number of single cells (ie, one positive electrode and an opposing negative electrode) electrically connected in parallel. This intermediate comb assembly 242 is best shown in FIG. 11 and has two combs. A conductive busbar member 244 with opposing surfaces (consisting of dense graphite)
and a plus deck frame 246 that is positioned almost surrounding the edge of this busbar member and creates an electric seal between adjacent cells.
The frame 246 is preferably f'fJFA.
1) Formed by injection molding VC around the edges of the part 244. A pair of opposing longitudinally extending Ws 247 are connected to this P
It can be used to provide a mechanical bond between the vC enclosure and the edges of the busbar member 244. A plurality of anode electrode assemblies 248 are fixed to the spaced vertical fii 249 on one external surface of the bus bar member 244 by IE L fitting or interference fitting. A plurality of cathode electrodes 250 are secured to other surfaces of the busbar member in a similar manner. Each of the anode electrodes 4111 and 248 are constructed according to the electrode assembly 200 of FIG.
; and 204, plus deck frame member 208 J> J
, and 210. A cell electrolyte distribution manifold 252 is ultrasonically welded or otherwise secured to the ICi portion of the frame 24G so that electrolyte is transported to the supply tube 216. Specifically, a protrusion 226 extending from portion 1i'1 of frame member 210 is inserted into a hole in weapon 254 of manifold 252. These protrusions 226 are then welded to the bottom 11+1254 of the manifold 252 by thermocompression to create a leak-tight bond. In order for each cell to be sealed separately, the 10th
A plastic backing plate 256, shown in the figures, is welded or otherwise secured to the busbar frame 246 in a fluid-tight connection. The return path for the electrolyte supplied to each cell is
It is provided with a collection cup 258 and a discharge serpentine plate 260 which channel the current flow from the cell and direct this electrolyte to a storage tank or sump. As in the case of other plastic frame members or parts, the collection cup 2
58 and the output serpentine vortex plate 260 are welded or otherwise secured (such as solvent bonding) to the receiving plate 256 in a fluid sealed bond. As illustrated in FIG. Cell distribution manifold 25
2 also has a top cover 262, which is secured to the weapon 254 by welding or solvent bonding. The important features of this manifold 252 are the weapon 254 and the top cover 26.
2 and a plastic perforated screen 264 extending along the entire length of the manifold. The pores of this screen 264 are selected to be suitably smaller than the pores of the protrusion 226 of the frame 1J 210 so that any particles that may interfere with the flow of fluid through the electrolyte supply tube 216 Moko's screen 264
will be compensated by. School ■-ゝnori-kai, I
It is composed of HI+7-I+, and [-I h7+l quotient], and is preferably curved into a substantially U-shape. The manifold 252 also includes suitable apertures 265 to vent gas that would otherwise accumulate within the manifold.
(as shown in FIG. 12) can be established (). Providing this opening 265 near the outer edge of the unit cell also allows a sufficient electrolyte flow to occur near the outermost electrode of the unit cell. In FIG. 10, the aforementioned plastic parts 252-264 are shown in an assembled condition as shown in the chlorine terminal comb assembly 240. This j-fukumoto terminal comb-shaped assembly 240
is similar in syntax to intermediate comb assembly 242 except for the following: "J straw, chlorine terminal comb assembly is connected to bus 2.
44 does not have a plurality of cathode electrodes 250 along one surface thereof. However, the chlorine terminal comb assembly 240 is connected to the busbar 244 to facilitate external electrical connections to the submodule 236.
Connect multiple electrical terminals mounted on the right. These electrical terminals are indicated generally by reference numeral 266 and are illustrated with respect to zinc terminal comb assembly 238. The zinc terminal comb assembly 238 has only one bus bar, the edges and outer surface of which are enclosed within a plastic frame, and a plurality of cathode electrodes affixed to the inner surface of the bus bar. In the assembled configuration, the anode electrode assembly 248 of the intermediate comb assembly 242 is connected to the cathode electrode 250 of the zinc terminal comb assembly 238.
and every other shade 41 of the intermediate comb assembly 242.
J) Electrode 2501,'') 21 elementary terminal comb-shaped phase solid 240
The anode electrode horizontal bar 248 and one d3 are inserted. Therefore, the anode electrode body 248 of the intermediate comb assembly 242, the negative electrode body 250 of the lead terminal comb assembly 238, etc.
forms one cell. Additionally, the cathode electrode 250 of the intermediate comb assembly 242 and the anode electrode assembly 248 of the chlorine terminal comb M1 solid body 240 form another cell of the submodule 236. Referring to FIG. 12, there is shown an "assembled" sub-7 joule cutaway perspective view of the battery stack 18 of FIGS. 2 and 3. This sub module 54 (1
4 is similar to Figure 10 in several respects.
Similar to 36. The main phase of these two sub-modules is that the rib module 236 has section II:i generally open to allow chlorine gas (as well as any other gases) to escape from the cell. However, the submodule 54 is generally closed at its top t to control fluid flow from the cells. The ribmodicols 54 are electrically connected in one row /J2
/Ifl! There is a cell C consisting of a cell J. These li
The cell is shown generally as f[3001,:J:. Referring further to FIGS. 13-16, several views of a zinc-terminated cell 300 for the SF module 54 are shown, particularly illustrating its Plus Snack II'' section 310. The In section is welded or otherwise sealed to the receiving box section 311 with three side bends to form a substantially closed section for the cell.
The partial section 310 has an electrolyte supply opening 312 to the right, which is connected to the electrolyte distribution pipe 88 via the supply pipe 313 of the Ill battery. A similar electrolyte connection can be seen in FIG.
0 of the cell 316 of the submodule 52 connected to the electrolyte distribution pipe 318.
314 is shown. The top d1 section 310 of the cell 300 also has an outlet opening 32
2, which is connected to the stepped canopy 32 via the exit pipe 326.
4. As best seen with respect to FIG. 14, the top section further includes a generally horizontally extending In wall 328 that is formed with a downwardly extending serpentine partition section 330. 330 is used in combination with the IJI outlet manifold 332 of the serpentine j14, and the bottom cover plate 334 which is firmly fixed to it.
As best seen in FIG. 6, chlorine gas and electrolyte solution can be flowed out of the cell 300. The top section 310 of the cell 300 further includes a 111 cell electrolyte supply manifold 338, which is generally comprised of a top cover 340 and a weapon 342 secured to each in a fluid-tight relationship. . The top section 340 extends from the upper cylindrical section 344 and from the top wall 328 of the top section 310.
The supply opening 312 is fitted into the cylindrical portion 344 with a 1:q movement. The top cover is formed with elongated downwardly extending partition portions 346 and 348. and these partitions are located at the bottom In+ 3
42 to direct a flow of electrolyte through manifold 338. A screen 350 is interposed between the top cover 340 and the weapon 342 to filter the flow of electrolyte to the cell 300. The weapon 342 has a plurality of holes 35.
2 is formed, and the protrusion 2 of the electrode meter 208 is passed through this hole.
26 extends and connects to the weapon), allowing the flow of electrolyte to flow into the chlorine type 4fj#, or into the 811 space between the β1 electrodes 202 and 204. Referring to FIG. 3, FIG. 4 J5, and FIGS. 9 to 16 at 51, it can be seen that all four of the four chlorine-type pairs included in the electric current solid body 200 of the battery device 1o are a3: The uniformity of electrolyte distribution is well explained. As shown in the figures mentioned above, the electrolyte circulation rib system 20 of the battery Vx ra 10 includes numerous large and small manifolds, serpentine tubes J3
and various branches of the judiciary, and their liberties are:
Compared to the relatively high fluid resistance provided by each supply pipe 216 (see FIG. 9) in the cell stack 18 - C1 the rather low fluid resistance for the amount of electrolyte designed to flow through those distribution pipes. The judiciary is designed to accept resistance. Thanks to this arrangement 81, approximately equal water pressure is maintained in all the cell manifolds 252 (see FIG. 11) and all the meandering groove illumination manifolds of each shib module (see FIG. 12, J3J, and FIG. 14). exists. Even though the one-knob modules 52 and 54 are not equal, there are approximately equal volumes. Therefore, the differential electrolyte pressures through each supply tube 216 are substantially the same. , and because all supply tubes 216 in the cell stack have the same length and inner diameter, all electrode assemblies 200 in each tube experience substantially the same flow rate. Similarly, the flow rate of the four-sided Mayu and distribution in the ff2 solution shield ring rib system 20 is relatively low compared to the flow rates they experience. Since (i-?J), the required water pressure difference L through the supply tube 216, and therefore the flow fit rate of electrolyte to the electrode assembly 200 to which that supply tube supplies electrolyte, is 7. during charging and T1 during discharging. With particular reference now to FIG. 15, cell 300 is shown including gas relief valve 354; The gas relief valve 354 is secured in a fluid 1.1 tight relationship to the top wall 328 of the cell.The gas relief valve 354 responds to the electrolyte level within the cell 300 to In particular, this escape valve 354 is used to selectively release gas from the single cell when the battery device 10 is in the pre-charging state.
It is advantageously used to release any hydrogen gas that may be present. The relief valve 354 is composed of a conical housing 356 having a hollow interior 357 in the shape of a circular ring 4, and a floating member 358 with a force. The housing 356 is formed with an opening 360 at its top for venting gas, and a pair of tongue members 362 at its bottom.
33 J, and 364 (best seen in Figure 16) are formed to attach these tongue members to the top wall 328. The floating member 3581 has a conforming shape to the inner surface 366 of the ring 356 so that the floating member resists the pressure exerted on it by the electrolyte. When moved upwardly into the airtight suspension, it will stop the flow of fluid from the single reservoir compartment. The floating member 358 is also formed with an upwardly extending rod portion 368 that guides the upward movement of the floating member into a sealed rest position with the housing 356. Since the float member 358 preferably has a hollow interior, the bottom plate 370 is joined to the interior portion of the float member to contain the trapped air therein. Also, single 'a
The top wall 328 of the pond section has an opening 372 for communicating fluid to the relief valve 354.
This opening is also made to be appropriately small to prevent the floating member from falling into the electrolyte level/J (to prevent the floating member from falling into the electrolytic solution level/J (to the left). However, this opening 372 does not have a suitable shape to allow ventilation when the member rests on the I0 wall 328. ) must be. During charging or discharging of the battery device, when the electrolyte is circulating through the battery device 4, the discharge manifold 332 for each 300 of the 11 cells is filled with electrolyte. The floating member 358 would then be moved upwardly to the Itil D 360 position. And when the i'i battery device is switched to a state-of-the-art state, even if J3 is at the end of charging or discharging (91, electrolyte, 1 balance P1 is stopped, the circulation of electrolyte is stopped. With the stop lever, 87> is reached.This causes 4Jl output manifold 332 σ)
The 't'+i solution level will drop -C-[J to the point where the opening 360 is reopened due to the downward movement of the floating member 358. When opening 360 reopens,
Both the gas present in the JJI outlet manifold 332 and the gas present in the gas space between the plate 334 and the seed part of the electrode frame member 208 are discharged from the 111 battery compartment via the escape valve i'354. will be done. This automatic 111
The zinc chloride device is particularly important when the battery device 10 is placed in a particularly low state after it has been charged, and it is important that the zinc This is because any hydrogen gas generated at the Ti electrode or cathode electrode 206 can be exhausted from the cell compartment. The relief valve 354 can also be configured such that, by appropriately selecting the method and density of the floating member 358, the buoyant floating member 358 is moved to the housing by capillary attraction or surface tension of the electrolyte after electrolyte circulation is completed. 356 and seal.”
Care should be taken not to leave it raised in the L engagement. Turning now to FIGS. 3 and 5, these figures also show that the valve modules 52 and 5 are located within the lower container 14.
4 is supported by: Plus deck pedestal 4 used for
00 is shown as an example. After the submodules 52 and 54 are fully assembled with the various electromagnetic fluid distribution and collection members coupled thereto, the pedestal 400 is inserted into the container 14 along the longitudinal rail 402. . Figure 3 also shows ribmodicol 52 d3 J, and 54
To illustrate the electrical connections made to the A set of four power terminals 404 are provided, one power terminal coupled to each end of one knob module 52 and 54. Each of these power terminals is a titanium coated copper bar 4.06 that is IM welded to a titanium cross bar 408. Butanium cross bars 408 are attached to a plurality of terminal posts 410 installed at each end of submodules 52 and 54.
) - once secured to modules 52 and 54;
Preferably, it is placed within a plastic (liquid injection resin) envelope that extends outside the container 14. The free ends of these power terminals 404 can then be connected to a suitable DC power source for charging the battery device 10 or to a suitable load for discharging the battery device. FIG. 3 also illustrates a single glass tube 412 that is used to house a suitable ultraviolet light source, shown in phantom at 414. A glass tube 412 extends outside the container to facilitate UV light exchange. The ultraviolet light source is adapted to react any hydrogen gas present in the gas space within the container 14 with the chlorine gas to form hydrogen chloride. Referring again to FIG. 2, storage subsystem 1 of container 12
6 and the battery stack 18 and electrolyte circulation subsystem 20 of the vessel 14 will be briefly 32 explained. While the battery device 1o is in the charging state,
The battery stack 18 will provide a continuous supply of chlorine gas. This chlorine gas is drawn from vessel 14 into 'fJ vessel 12 via conduit 26 by gas/ice pump P2. Pump P2 then mixes the JM fk gas with the cold IJI liquid in vessel 12 to form chlorine hydrate. If the battery is in a discharging state, -i? \/ 11:l Ijil 111h TiT
1 (Ij receiving Jj, A convex 9.) c, so that the warm electrolyte of c, is pumped through the ice decomposition heat exchanger 1-I
Ru. In this, J, C1 hydrate is gradually decomposed, and Jg
Continuous supply of cable gas begins m1. When valve v2 is open, the chlorine gas released into vessel 12 is directed to
It is returned to the container 14 via τ24. And this JM
The hydrogen gas supply is injected into the electrolyte circulation subsystem 2o where the gas dissolves into the electrolyte that is being distributed to the cell stack 18. At the end of discharge, in J3, all of the chlorine hydrate is decomposed and the j]A water gas is returned to the battery stack 18, where 8! I will be expended. FIG. 17 shows the equipment arrangement within the storage system 16 shown in FIG. 1 and FIG. 2.
It is a fEl perspective view. The storage section 16 is housed in a short cylindrical case or container 12, and is mounted on the top of the battery stack container 14 as shown in FIG. The container 12 has an integral domed end 6
00, and the other end is closed with a dome-shaped cover 602, which is bolted to a flange 604. In operation, container 12 is almost entirely filled with liquid (preferably water), leaving a relatively small gas space 605, as indicated by liquid level line 606 in FIG. Components located within or on the storage vessel 12 include:
Gas/ice pump 1] 2, filter package F, pressure control orifice 622, ice generation heat exchanger 1-IX 1
and decomposition heat exchanger HX 2. Various features and operating characteristics of these components are discussed below. The gas/ice pump] 2 and the electric drive motor 608 attached thereto are mounted on a protrusion 610 of the dome-shaped cover 602.
will be mounted on. Pump l) 2 is of a "plug-in" design with the motor wire magnetically coupled to the pump shaft by a Plano-Chick pump cover 612, so that both the motor shaft and the pump shaft are stored. It does not protrude from the outer wall of the container 12. Pump P2 is an Ingersoll Rand external gear or spur gear type with plastic gears and housing and graphite bushings. Pump P2 directly pumps container 12 from conical nozzle 614.
is discharged into the gas space 605 at the top of the . The suction portion 616 of pump P2 is inserted or coupled to the rear right into an inlet fitting or coupling 618 that is rigidly mounted within the container 12. The gas of the battery stack 18 coming through the conduit 26 and the liquid from the storage container 16 pass through the connection 618 to the pump 1]2.
supplied to The cooled liquid (preferably water) is drawn from the liquid or water reservoir 620 of the container 12 through a tube-shaped heat exchanger 1''xl. In order to prevent the muddy ice crystals in the water storage tank 620 from being drawn into the heat exchanger t-IXI J5 and the pump P2, a filter package in the form of a separator plate is used. The filter F is made in one shape in the double wall 1 and is connected to the water storage tank 6.
20. Filter F is constructed of PVC M4 with a diameter of 1 mm stretched over a hardened annular plastic frame and covered with a Teflon felt cloth cylinder to prevent any ice from forming in the space between the double walls of the cylinder of Filter F. Chemical crystal 1
It also effectively prevents acceptance. Water (enters the heat exchanger 1-I x 1 from the space between the cylindrical double walls of the filter F through the A refill 622, which has a size that accommodates the required liquid flow rate, and enters the heat exchanger) -IX
Heat exchanger 1' As shown in many of the drawings, it is preferable to assemble a simple inner tube assembly, which is preferably shown in FIG. Preferably, the outer surface of the inner tube is coated with a high-flux coating, commercially available from Conion Carbide = 1-Poration, to enhance nucleate boiling and increase the heat transfer coefficient. 24f',
I refrigerant 81 by effectively increasing from 10 to 8
The heating required for boiling can be dramatically reduced. By using such a coating, the heat exchanger 1''
l can be made even smaller in volume than would otherwise be possible. The refrigerant used in the heat exchanger 1'Xl is preferably Freon 12 and is provided via refrigerant supply d3 and return pipes 32 and 34, which are connected to the pressure nozzle J'A bushings. Domed end 600 of storage container 12
is shown through the shell. As shown in Fig. 2 and Fig. 17, a coil 6 of cold 14mm, heat exchanger 1%
24 , and the storage liquid flows through the inner tube of ] 624 . The device mounted inside the storage container 12 is mounted on a self-seating support frame or pedestal (as shown) fixed on the curved inner surface of the container. The 14 eel support frames (31, heat exchanger 1-I
1, J, and l-I. 11 can be erected outside the storage container 12 so that the storage container 12 can be opened. The bushings for the two refrigerant pipes 32 and 34 and the heat exchanger HX2 (Fig.
The various features of the device of the storage container 12, such as the two bushings for the tubes 28 and 30 (see Figure 9), are identical to each other for the storage container 12. 17, 19 and 20. By using the device N at point H, such as a supporting frame, it is not necessary to carry out any assembly operations inside the storage container 12. The various geometries of cracking heat exchangers shown in Figure 1 can be made up of a length of tube (preferably 12
．． 7mm or 15.9mm (1/2 in or 5
/8in) outer diameter titanium whistle) is bent into the desired shape or pattern. For reasons explained in detail below, the coil shape chosen for heat exchanger HX2 is not used and is capable of depositing electrolyte from heat exchanger HX2: It should be a sea urchin. See Figure 19. Figure 20 shows a heat exchanger HX designed to ensure such proper drainage.
2, two preferred coil patterns are shown. Experience has shown that if J: for example, in the approximately horizontal = 1 illumination pattern for heat exchanger HX 2 shown in FIG. It was found that the government was not able to effectively carry out its activities. As previously mentioned, the storage container 12 itself is preferably made of FRP (glass fiber reinforced plastic);
A PVC (polychloride) liner is glued to it. The temperature within the storage vessel 12 is preferably maintained at about 10° C., which is one degree lower than the typical ambient temperature for indoor installations of battery devices, thus improving the energy efficiency of the overall system. 1. Preferably, most of the external surface of the storage container is wrapped in thermal insulation. -IB- In a suitable example, 3Bmm of urethane foam designated by reference numeral 628
approximately 80% of the exterior of container 12 in a layer of (11/2 in)
A thin 3.2IIvR (1/8 in) coating is applied to the urethane foam to further protect it from scratches.
FRP can be wrapped and covered. In the battery device 10 of the present invention, the preferred electrolyte is a 2 molar concentration of zinc chloride (measured once the battery device 1o is fully discharged), about 4 molar concentration of potassium chloride and A supporting salt with about 1 molar concentration of thorium (i.e., conductivity improvement) is included to increase the efficiency of the overall cell system. During normal operation of the battery device 10, the stack container 1
The temperature of the electrolyte in 4 is preferably about 30°C and 40°C.
was maintained between. The electrolyte from the sump is continuously circulated through heat exchanger 1-I
X 2 10'cL during the entire passage: 1.1 = cold 7.
(Since the support salt is not added to +, precipitation of the supporting salt in the electrolyte solution does not occur normally at that time. However, the heat exchanger 1-I
If the electrolyte solution in the heat exchanger cools down to around 8 Il while X 2 is maintained in the storage container and stops for a long time, the precipitation of supporting JM and the resulting decomposition heat exchange occur. Blockage of vessel 1-I One major problem was that the electrolyte contained in the container remained in the container. In order to eliminate such problems, the zinc chloride battery device shown in the prior art has a decomposition heat exchanger HX2 which does not require the flow of electrolyte to pass through it for one hour! During the iJ period, the steps had been repositioned to cover the self-tJl liquid. To do this without adding any significant additional cost, complexity, or control equipment (e.g., control valves and/or pumps) to the battery system, the battery system 10 includes: The heat exchanger 1'' of the storage rib system 16 is now positioned higher than the reservoir 40 associated with the battery stack 18.
fff, when the electrolyte does not need to flow through the heat exchanger IX2, the electrolyte flows from the heat exchanger to the reservoir 40.
It is m DIed so that it flows back to the beginning. This is particularly important if the storage vessel 12 is positioned completely above the stack vessel 14 as shown in recent battery device designs of FIGS. 1, 2 and 20. : It will be achieved. FIG. 18 is a schematic illustration of a self-contained JJ14M heat exchanger concept with reservoir 630 located above the electrolyte level in sump 40. Electrolyte pump P1, which can be seen with reference to FIG. 18, supplies electrolyte to stack 632. At the end of the discharge condition of the zinc-chloride battery cycle, the pump [] 1 is also normally at I'! during all other times of the battery cycle. Fltllll decomposition 11i1J
After listening to the control valve V1, the electrolyte is supplied to the heat exchanger 11X2 through the conduit 634. heat exchanger)-I
The rate of heat imparted to the liquid in the storage vessel 630 by 2 determines the rate at which the chlorine hydrate in the storage vessel will decompose and generate heat. Control valve V1 is intermittently opened and closed during discharge conditions to adjust this heat transfer rate. When the flow of electrolyte is blocked by control valve v1, the electrolyte in heat exchanger 1-I X 2 has a conductivity of 636
The book is published into the 'a reservoir 40 through the 'a' storage. As will be understood by those skilled in the art, if the heat exchanger 1"x2 is a waste sump 40J:
If the tube is located high enough, has a sufficient slope, and the tubing has a sufficient inner diameter, the electrolyte will naturally flow therefrom. In particular, the electrolytic solution used in lead chloride battery devices has a density very close to that of pure water. However, in order to facilitate faster drainage of the relatively small diameter tubing typically used in heat exchanger HX2, a connection between the outlet of pump P1 and the inlet 640 of heat exchanger 1-I A venting device 638 is added to allow gas to exchange with the electrolyte and enter the heat exchanger as the electrolyte exits the heat exchanger IX2. Gas is drawn from the gas space 642 of the stack vessel 14, preferably as shown in FIG. In the battery device shown in FIG. 18 and using the disassembly valve 11 valve v1 basically arranged as shown in FIG. 18, the vent hole 638 must be located downstream of the control valve V1. According to a suitable embodiment of the zinc chloride battery device of the present invention, a ventilation device 6381 is provided with a hole having a diameter of 1 and 6 cylinders < 1/16 inch) installed in a conduit 634, and a stack container 1
It is connected to a gas space 642 within 4. Those skilled in the art will appreciate that larger or smaller brush cutting holes could be used as the vent holes 638. For example, 0, 8rtm (1732 stitches 1)
Although it is possible to use a hole of 166M (
Pores of 1/16 in.) appear to be preferred. After all, any small particles or particles that may be present in the electrolyte
This is because it is thought that blockage due to foreign matter is rare. , 1. The advantage that small holes, such as 6 mm (1/16 in) diameter, have over fairly narrow holes, such as 8 mm (5/16 in) diameter, is that their liquid volume capacity reduces the electric current passing through the heat exchanger. - The electrolyte flow returned to the reservoir 40 through the vent hole 638 is J! This means that we have to accept the considerable energy loss. Nevertheless, the gas volume capacity of the vent 638 to such a small hole is 151, before the electrolyte in the heat exchanger HX2 has cooled sufficiently to cause a slow precipitation of conductivity improving salts. Thoroughly drain the electrolyte from heat exchanger 1 (x2).
The capacity is large enough to overflow. Figures 18 and 19 and Figure 20 show a heat exchanger HX 2 G of self-waveform U1, preferably in three parts (
? This indicates that 4 will be created. J, that is, entrance part 6
40 and the exit part 644, the population part and the exit part 1
In order to prevent the Ti electrolyte from remaining in the heat exchanger 11 It is preferable for the map to slope continuously downward. The angle of this inclination is that it is the heat exchanger HX2
As long as there is no electrolyte left in the IJ, and any significant precipitation is sufficient to allow the electrolyte to exit the IJ in a relatively unscrupulous manner, the electrolyte should be changed before cooling. There is no problem with U. The optimum slope d3 and shape of the heat exchanger 1-I
The length of the pipe system used, and the quality of the connection between the heat exchanger and the electrolyte pump (1) and the electrolyte pump (1). , depending on the size of the vent 638 or A-rifice. All of these details are within the scope of the present invention. The venting device 638 is not limited to being continuously connected to the gas space as shown in FIG. 18, but may also be a conduit that is opened and closed as needed by the use of a control valve. 6371 L-iG9rono+11 f:r
It would also be preferable for the z1 holes to use control valve provisions for ventilation. After all, such vents are cheaper, simpler, and inherently automatic in operation. As seen in FIG. 18, the disassembly control valve V1 and the vent hole 6
Guide between 38? Some electrolyte may remain in the ff634. Because the conduit 634 is outside the storage vessel 12 and is exposed to relatively high ambient temperatures, precipitation therein is not a problem. Another advantage of the basic self-liquid heat exchanger system shown in FIG. It is to fully utilize the natural motion h1 of the electrolyte flowing through the vessel 11x2. 1 and 2 illustrate a preferred embodiment of the vent 638 and its piping system (the disassembly control valve V1 and vent 638 are shown schematically in FIG. 2 as A-refit 648). J as shown: located outside both the storage container 12J3 and the stack container 14. Conduits 24, 26
, 2863 and 30, valves v1 and v2, vent hole 638 J5, and other devices shown in FIGS. make it easier. Figure 19, J and 20
The figures show preferred embodiments of self-draining, resting devices and coil patterns for heat exchangers 1-I x 2, respectively. Self-draining heat exchange 2:1- as described above for FIG.
Testing of the IX2 device has shown it to be very effective in preventing salting out in the heat exchanger HX2 and thereby preventing blockage problems. FIG. 20 shows another embodiment of a storage system, which is designed for a five person commercial facility, such as a load averaging application in an electrical facility. The operating principles and composition techniques of the battery device shown in FIG. 20 are basically the same as those shown for the battery device of FIG. The upright position of storage vessel 12 in FIG.
We propose a stacking arrangement with an extremely good volume ratio for multiple battery devices used in large-scale applications such as average battery equipment. The energy capacity of the battery with a considerably high energy capacity L is shown in Figure 21.
d, each individual battery device shown in FIG.
m (battery stack in Figure 2 of the 72nd ring) shown here! iJ: sea urchin) to 234 cm (92 inches). Similarly, 3
heat exchangers 1-I X 1, l-I X 2, (I
j J: and any other parts (i) are increased in size to accommodate the increased energy capacity 1i. However, the present invention is susceptible to modifications, changes and changes without departing from the inherent scope or legitimate meaning of the appended claims. [Effects of the Invention] According to the present invention, in at least one unit cell that generates gas and an electrochemical device that is in communication with the unit cell, the gas generated from the unit cell is selected. can be utilized to keep the electrochemical device in optimal condition.

[Brief explanation of drawings]

FIG. 1A is a side view of an embodiment of a zinc oxide battery device according to the present invention. FIG. 1B is a front view of the battery device similar to FIG. 1Δ. FIG. 2 is a schematic diagram of the battery device shown in FIG. 1Δ and FIG. 1B. FIG. 3 is a cutaway perspective view of the stack and electrolyte circulation rib system of the battery device shown in FIGS. 1 and 2. FIG. FIG. 4 is a schematic diagram of the electrolyte circulation leave system shown in FIGS. 2 and 33. FIG. 5 is a front view of the stack J and electrolyte circulation rib system shown in FIG. 3 with end plates removed. FIG. 6 is a partial plan view of the electrolyte circulation distribution manifold of the electrolyte circulation rib system. FIG. 7 is a partial cross-sectional view taken along line 7--7 of the manifold shown in FIG. FIG. 8 is a diagram comparing parasitic current values associated with two electromagnetic fluid circulation plans. FIG. 9t is an expanded 1+11 perspective view of the electrode assembly forming the basic 41'+5 1:1 stack of the cell stack shown in FIGS. 2 and 3; FIG. FIG. 10 is a partially exploded view of an "open" module of a zinc chloride battery stack. FIG. 11 is a perspective view of the comb assembly shown in FIG. 10 and used in the module. FIG. 12 is a cutaway perspective view of a closed J-leave module of the enriched zinc battery stack shown in FIGS. 2J and 3. FIG. Figure 14 is a partial top view of the sub module taken along line 14-14 of the sub module shown in Figure '13. Zabmojikor line 1
It is a 01 side view along 5-15. Figure 16 shows line 1 of the rib "ji" shown in Figure 15.
6-'+6 is a horizontal plane view along 6-'+6. FIG. 17 is a cutaway perspective view of a storage subsystem using a conventional decomposition heat exchanger. FIG. 18 is an 11-fold schematic diagram of a self-published liquid type thermal molecular fC heat exchanger for a zinc chloride battery device. FIG. 19 is a cut-away perspective view of the storage rear system for the battery device shown in FIGS. 1 and 2. FIG. FIG. 20 shows another embodiment of the Fussa zinc battery device according to the present invention. FIG. 21 is a perspective view of a plurality of high-density arrays of batteries of the type shown in FIG. 20. DESCRIPTION OF SYMBOLS 10... Zinc chloride battery device, 12... Upper cylindrical container, 14... Lower cylindrical container, 16... Chlorine hydrate storage system, 18... Battery stack, 20...
・Electrolyte circulation leave system, 24, 26, 28.30
...Fluid conduit, 32.34, 36.38... Refrigerant conduit, 40...''yi electrolysis tank (liquid reservoir), I
') 1... Electrolyte pump, P2... Gas/ice pump, 44... Electric motor, 46... Electrolyte filter, 50... Electric M liquid distribution-l Nibold, 52.54
...Battery stack/sub module, 58...Inner tube of slip 111 hand, 60...Outer tube of slip joint, 66...Wire mesh filter, 68...Protection envelope, 7
0... 4 needles, 72... End cap of outer tube, 74... Electrolyte passageway, 76... Conduit, 78...
End, 80, 82, 84.86... Branch claw (-J body,
88.94...Inlet distribution piping, 100,102...Outlet distribution piping, 90...Left half of sub module, 92...
・Sub module right half, 96.98... Single cell battery
Nm supply pipe, 104... stepped canopy, 106... 1 exit hole, 108... JJI exit pipe, 110... opening,
112... Parasitic current distribution curve (prior technique 1 ji), 1
14... Parasitic current distribution curve (device of the present invention), 200...
...Battery assembly, 202.204...Anode chlorine electrode (
porous graphite), 206... cathode zinc electrode (dense black 1)
), 208°210...Plastic frame member, 212
．． 214... fM of plastic frame, 216... Electrolyte supply port, 220... Chlorine gas discharge hole, 222,2
24... Spacing rib, 216... Hole with hole for fitting electrolyte pump, 232... Anode separation part, 23
4...Top water '8p flange part, 236...Battery stack ribbed joule, 238...Zinc electrode comb-shaped assembly, 240...Thoughts'ai pole comb-shaped assembly, 242
... Bipolar intermediate comb-shaped phase solid, 244 ... Generatrix β (January, 246 ... Plastic frame, 2
47...Fix the busbar to the frame, 248-Ffl
Pole m' @ 17.249- ICI PA section vertical surface, 252...11i battery electrolyte distribution unit, 254...distribution manifold weapon, 256...plus deck receiving plate, 258 ... Electrolyte collection cup, 26
0... Electrolyte discharge meandering 114 plate, 262... 1f1
Part cover, 264... Porous screen, 265...
Gas release hole, 266...External electrical connection terminal, 300
...111 Battery, 310... Plus Deck Ki section, 311... Receiving box section, 312... Electrolyte supply port, 313... Supply fi YR1322... Electrolyte outlet, 324...・Step-like large stack, 326... Electrolyte outlet pipe, 328... 10 layers, 330... Meandering partition, 332
...1) 1-output manifold, 334...bottom plate, 336
...Exhaust manifold opening, 338...Electrolysis...
Weapon, 344... Upper cylinder part, 346, 348...
・Partition part, 350...Filtration screen, 352...
・Screen hole. Agent Asa 4・l Ko F/g-5 Lyguri, father-in-law<n'ft Hori f-16 F-18 I-79

Claims (8)

[Claims] (1) an electrochemical device having at least one cell in which gas is generated and an electrolyte in communication with the cell, and the cell and at least a portion of the electrolyte; and selectively extracting 4111 the gas from the interior of the compartment in response to the level of the electrolyte in the compartment. - a device associated with the compartment device for the purpose of: (2) The evacuation device includes a relief valve having a flow member actuated in response to the level of the electrolyte in the compartment device [electrochemical according to claim 1] Device. (3) When the level of the electrolytic solution is above a predetermined level, the float member closes the relief valve to prevent the gas from coming out; When the level of gas is below the predetermined level J, the relief valve is turned on to prevent one part of the gas from flowing out.
An electrochemical device according to claim 2, which includes: (4) having a plurality of electrically connected unit cells, and a zinc deposit is present on the cathode electrode of the plurality of unit cells;
and when an aqueous zinc chloride solution is in communication with the plurality of cells, hydrogen gas is generated, and a device for circulating the zinc chloride solution through the plurality of cells is heated. In a zinc battery, a device for defining a substantially closed compartment within the battery that includes the plurality of cells and at least a portion of the electrolyte; A J Fussa Jlli lead-acid battery characterized by comprising: 1) a device 5 related to the partitioning device for selectively releasing the water-based gas from inside the partitioning device in response to the level of the liquid; . 5. The zinc chloride battery of claim 4, wherein the IJ1 outlet device includes a flow 1 relief valve that is activated in response to the level of the electrolyte in the compartment. (6) In the flow 1 to part 1, when the level of the electrolyte is above a predetermined level, the relief valve is closed to stop the discharge of the gas, and the level of the electrolyte is increased. The zinc chloride battery according to claim 5, wherein when the level is below the predetermined level, the relief valve is opened to allow one drop of the gas to escape. (7) An improved metal-halogen battery device comprising: a plurality of unit cells having anode and cathode electrodes that are separated and operate to generate hydrogen sludge; a device for tubing the electrolyte flowing through the plurality of Ill cells; a substantially closed compartment containing at least a portion of said electrolyte, said compartment having a 1" section, wherein the electrolyte level in said compartment is pre-determined. A gas relief valve is rigidly secured to said top section for venting hydrogen gas from said compartment upon lowering to a determined level. (8) The waste relief valve has a hollow interior and an orifice that communicates with the hollow interior and is provided at the upper nozzle, is firmly fixed between the top parts 8, and partially protrudes. The housing has a shape that almost fits into the hollow interior, and has a buoyant flow 1 member C located in the hollow interior, and the flow 1 to 1 members are engaged with the housing interior in a fixed state. and a lower position where the orifice is in flow communication with the compartment and discharges hydrogen gas from the compartment, depending on the level of the electrolyte. 14. Range of permission requirements g87 Full bending H1-
1-gen battery device (()) The float member has a round button shape, and has a stem portion that extends upwardly and partially enters the orifice. battery device.